CN110002432B - Preparation method of graphene with multilevel structure - Google Patents
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Abstract
The invention belongs to the technical field of nano composite materials, and particularly relates to a multi-level structure graphene, and a preparation method and application thereof. The invention provides a preparation method of multi-level structure graphene, which comprises the following steps: vertically growing a copper hydroxide nanorod on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material; calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material; reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material; depositing graphene on the copper substrate/copper nanorod array by using a chemical vapor deposition method to obtain a copper substrate/graphene material; corroding the copper substrate in the copper substrate/graphene material to obtain the multi-level structure graphene which is free from curling and stacking and excellent in conductivity.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a multi-level structure graphene, and a preparation method and application thereof.
Background
The graphene nanosheet is a hexagonal honeycomb-shaped lamellar material formed by sp2 hybridized orbits of carbon atoms, and the structure of the graphene nanosheet endows the graphene nanosheet with a plurality of excellent physical and chemical properties, such as ultrahigh specific surface area, good mechanical property, electric and thermal conductivity, chemical stability and the like, so that the graphene nanosheet is a hot point of research since being discovered in 2004, and the application field of the graphene nanosheet also relates to the square surface in life.
The graphene nanosheets with a single layer or a small number of layers are easy to curl, stack and agglomerate due to the large surface energy, so that the physical and chemical performances of the graphene nanosheets are greatly limited, and therefore, how to ensure the conductive performance of the composite material is especially important for designing the graphene composite material with the shape-controllable micro-nano structure.
Disclosure of Invention
The invention aims to provide a multi-level structure graphene, a preparation method and an application thereof, wherein the multi-level structure graphene is free from curling and stacking phenomena and excellent in conductivity.
In order to achieve the above object, the present invention provides a method for preparing graphene with a multilevel structure, including the following steps:
vertically growing a copper hydroxide nanorod on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material;
calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material;
reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material;
depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain a copper substrate/graphene material;
corroding the copper substrate in the copper substrate/graphene material to obtain the multi-level structure graphene.
Preferably, the graphene with the multilevel structure comprises a graphene nanotube and a graphene nanosheet, wherein the length of the graphene nanotube is 20-50 nm, and the thickness of the graphene nanosheet is 5-10 nm.
Preferably, before the step of vertically growing the copper hydroxide nanorods on the copper substrate by using the chemical oxidation method, the method further comprises washing the copper substrate with hydrochloric acid and water alternately for several times, wherein the copper substrate is a copper sheet, a copper wire mesh or a copper foam.
Preferably, the step of vertically growing the copper hydroxide nanorods on the copper substrate by using a chemical oxidation method to obtain the copper substrate/copper hydroxide nanorod array material specifically comprises the steps of immersing the copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing for 1-24 h at room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1.
preferably, the step of calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain the copper substrate/copper oxide nanorod array material specifically comprises calcining the copper substrate/copper hydroxide nanorod array material in an argon atmosphere at 500-600 ℃ for 1-3 h to obtain the copper substrate/copper oxide nanorod array material.
Preferably, the step of reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain the copper substrate/copper oxide nanorod array material specifically comprises,
preparing a reducing agent solution from sodium hydroxide, a reducing agent and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material.
Preferably, the reducing agent is one of glucose, hydrazine hydrate, sodium borohydride, ascorbic acid and oxalic acid.
Preferably, the step of depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain the copper substrate/graphene material specifically comprises,
ultrasonically cleaning the copper substrate/copper nanorod array material;
placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm;
adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas;
and in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain the copper substrate/graphene material.
The invention further provides the graphene with the multilevel structure, which is prepared by any preparation method.
The invention further provides application of the graphene with the multilevel structure in a super capacitor, a conductive coating or a conductive ink.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of multi-stage structure graphene, which comprises the steps of vertically growing copper hydroxide nanorods on a copper substrate surface, reducing the copper hydroxide nanorods into copper nanorods through multiple reduction treatments, depositing graphene on the surfaces of the copper substrate and the copper nanorods, depositing on the copper substrate surface to obtain a graphene lamellar structure, depositing on the surface of the copper nanorods to obtain a graphene tubular structure, wherein the graphene lamellar structure is vertical to the graphene tubular structure, the graphene lamellar structure and the graphene tubular structure are prepared in one step by a chemical vapor deposition method, the deposition thickness is uniform, the graphene lamellar structure and the graphene tubular structure are integrated, the two structures are not simply spliced, the phenomena of graphene stacking and agglomeration cannot occur, and the probability of defects of a graphene material is reduced.
And the graphene lamellar structure and the graphene tubular structure form a three-dimensional conductive network system, electrons can freely migrate on the graphene lamellar structure and can also be quickly transferred along the axial direction of the graphene tubular structure, and the conductivity is excellent.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a copper substrate/graphene material provided in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of graphene with a multilevel structure provided in an embodiment of the present invention;
wherein, 100-copper substrate/copper nano-rod array material; 200-graphene with a multilevel structure.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
With reference to fig. 1 and fig. 2, in one aspect, an embodiment of the present invention provides a preparation method of graphene with a multilevel structure, including the following steps:
s01, vertically growing copper hydroxide nanorods on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material;
s02, calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s03, reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material;
s04, depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain a copper substrate/graphene material;
and S05, corroding the copper substrate in the copper substrate/graphene material to obtain the multi-level structure graphene.
The embodiment of the invention provides a preparation method of multi-stage structure graphene, which comprises the steps of vertically growing copper hydroxide nanorods on a copper substrate surface, reducing the copper hydroxide nanorods into copper nanorods through multiple reduction treatments, depositing graphene on the surfaces of the copper substrate and the copper nanorods, depositing on the copper substrate surface to obtain a graphene lamellar structure, depositing on the surface of the copper nanorods to obtain a graphene tubular structure, wherein the graphene lamellar structure is vertical to the graphene tubular structure, the graphene lamellar structure and the graphene tubular structure are prepared in one step by a chemical vapor deposition method, the deposition thickness is uniform, the graphene lamellar structure and the graphene tubular structure are integrated, the two structures are not simply spliced, the phenomena of graphene stacking and agglomeration cannot occur, and the probability of defects of a graphene material is reduced.
And the graphene lamellar structure and the graphene tubular structure form a three-dimensional conductive network system, electrons can freely migrate on the graphene lamellar structure and can also be quickly transferred along the axial direction of the graphene tubular structure, and the conductivity is excellent.
In the embodiment, the graphene with the multilevel structure is deposited on the copper substrate/copper nanorod in one step by a chemical vapor deposition method, so that the obtained graphene with the multilevel structure is free from stacking and excellent in conductivity.
The graphene with the multilevel structure comprises a graphene nanotube and a graphene nanosheet, wherein the length of the graphene nanotube is 20-50 nm, and the thickness of the graphene nanosheet is 5-10 nm.
Specifically, the graphene tubular structure is a graphene nanotube, the graphene lamellar structure is a graphene nanosheet, the thickness of the graphene nanosheet is 5-10 nm, and the graphene nanosheet is a single-layer graphene nanostructure, so that the stacking phenomenon is further prevented; the length of the graphene nanotube is 20-50 nm, the length of the graphene nanotube is less than 20nm, the length of the graphene nanotube is too short, and the possibility of stacking phenomenon is high; the length of the graphene nanotube is greater than 50nm, and the higher the length of the graphene nanotube is, the higher the possibility that the graphene nanotube is broken or defective is.
Wherein, before step S01, the method further comprises washing the copper substrate with hydrochloric acid and water alternately for several times, wherein the copper substrate is a copper sheet, a copper wire mesh or a copper foam.
Washing the copper substrate by using hydrochloric acid and water alternately, and cleaning the surface of the copper substrate to remove impurities on the surface of the copper substrate; the concentration of the hydrochloric acid can be 2-5 mol/L.
The step S01 specifically comprises the steps of immersing the copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing at room temperature for 1-24 h, alternately washing with water and ethanol for several times, and drying to obtain a copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1. wherein, the ethanol can adopt absolute ethanol; the drying may be carried out by air drying.
And S02, specifically, placing the copper substrate/copper hydroxide nanorod array material in an argon atmosphere, and calcining at 500-600 ℃ for 1-3 h to obtain the copper substrate/copper oxide nanorod array material. Calcining in inert gas atmosphere to prevent other impurity by-products, and the sintered structure is relatively stable.
Step S03 specifically includes preparing a reducing agent solution from sodium hydroxide, a reducing agent, and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material. Through microwave hydrothermal, a reaction system is heated more uniformly, the reaction time is shortened, and the reaction is fully performed through the control of temperature and time.
Preferably, the reducing agent is one of glucose, hydrazine hydrate, sodium borohydride, ascorbic acid and oxalic acid. The raw materials are easy to obtain, and the preparation is more convenient.
Wherein, step S04 specifically includes: ultrasonically cleaning the copper substrate/copper nanorod array material;
placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm;
adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas;
and in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain the copper substrate/graphene material. The deposited graphene material has uniform film thickness and stable film structure.
Preferably, the carbon source gas is one of methane, ethylene and acetylene; the carbon source gas is easy to obtain and the operation is convenient.
The embodiment of the invention also provides a graphene with a multilevel structure, which is prepared by the preparation method of the graphene with the multilevel structure in any embodiment of the above embodiments.
The multi-level structure graphene is uniform in thickness, is not easy to stack and agglomerate, and has excellent conductivity compared with the traditional graphene sheet layer.
In yet another aspect of the embodiments of the present invention, there is provided an application of a graphene with a multilevel structure in a supercapacitor, a conductive coating or a conductive ink.
The invention is further illustrated by the following specific examples:
example 1
A preparation method of graphene with a multilevel structure comprises the following steps:
s101, washing a copper sheet for multiple times by using 4mol/L hydrochloric acid and water alternately, immersing the washed copper sheet in a mixed solution of 200mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 12h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s102, calcining the copper substrate/copper hydroxide nanorod array material for 2 hours at 550 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s103, mixing and dissolving 8g of sodium hydroxide and 8g of glucose in 80mL of water, adding the copper substrate/copper oxide nanorod array material into the water, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction for 1h at 160 ℃, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing with water and absolute ethyl alcohol for several times respectively, and drying at 60 ℃ for 40min to obtain the copper substrate/copper nanorod array material;
s104, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 20min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 1000 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 20sccm and argon with the flow rate of 800sccm, then adjusting the flow rate of the hydrogen to 100sccm, introducing methane gas at the flow rate of 30sccm, keeping the temperature for 15min, turning off the hydrogen and the methane gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/graphene material;
s105, immersing the copper substrate/graphene material into 0.5mol/L ferric chloride solution for corrosion, standing for two days, centrifuging after the copper substrate is corroded and disappears, washing with water for several times, and drying the obtained black solid at 60 ℃ for 30min to obtain the graphene with the multilevel structure.
Example 2
A preparation method of graphene with a multilevel structure comprises the following steps:
s201, washing a copper sheet for several times by using 4mol/L hydrochloric acid and water alternately, immersing the washed copper sheet in a mixed solution of 100mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 12h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s202, calcining the copper substrate/copper hydroxide nanorod array material for 3 hours at 500 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s203, mixing and dissolving 4g of sodium hydroxide and 8g of ascorbic acid in 80mL of water, adding the copper substrate/copper oxide nanorod array material into the water, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction for 2 hours at 120 ℃, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing the solid with water and absolute ethyl alcohol for several times respectively, and drying at 50 ℃ for 60min to obtain the copper substrate/copper nanorod array material;
s204, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 10min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 800 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 10sccm and argon with the flow rate of 600sccm, then adjusting the flow rate of the hydrogen to 80sccm, introducing ethylene gas at the flow rate of 10sccm, keeping the temperature for 20min, turning off the hydrogen and the ethylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/graphene material;
s205, immersing the copper substrate/graphene material into 0.1mol/L ferric chloride solution for corrosion, standing for two days, centrifuging after the copper substrate is corroded and disappears, washing with water for several times, and drying the obtained black solid at 50 ℃ for 50min to obtain the graphene with the multilevel structure.
Example 3
A preparation method of graphene with a multilevel structure comprises the following steps:
s301, alternately washing the copper sheet with 4mol/L hydrochloric acid and water for several times, immersing the washed copper sheet in a mixed solution of 300mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 1h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s302, calcining the copper substrate/copper hydroxide nanorod array material for 1h at 600 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s303, mixing and dissolving 16g of sodium hydroxide and 8g of oxalic acid in 80mL of water, adding the copper substrate/copper oxide nanorod array material, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction at 200 ℃ for 0.5h, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing with water and absolute ethyl alcohol for several times respectively, and drying at 80 ℃ for 20min to obtain the copper substrate/copper nanorod array material;
s304, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 30min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 900 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 30sccm and argon with the flow rate of 1000sccm, then adjusting the flow rate of the hydrogen to 120sccm, introducing acetylene gas at the flow rate of 50sccm, keeping the temperature for 10min, turning off the hydrogen and the acetylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/graphene material;
s305, immersing the copper substrate/graphene material into 1mol/L ferric chloride solution for corrosion, standing for two days, centrifuging after the copper substrate is corroded and disappears, washing with water for several times, and drying the obtained black solid at 80 ℃ for 20min to obtain the graphene with the multilevel structure.
The present invention has been described in further detail with reference to the specific embodiments thereof, and it should be understood that the foregoing is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, but rather that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of graphene with a multilevel structure is characterized by comprising the following steps:
vertically growing a copper hydroxide nanorod on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material;
calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material;
reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material;
depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain a copper substrate/graphene material, which specifically comprises the following steps: ultrasonically cleaning the copper substrate/copper nanorod array material; placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm; adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas; in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain a copper substrate/graphene material;
corroding the copper substrate in the copper substrate/graphene material to obtain the multi-level structure graphene.
2. The method for preparing graphene with a multilevel structure according to claim 1, wherein the graphene with a multilevel structure comprises a graphene nanotube and a graphene nanosheet, the graphene nanotube has a length of 20-50 nm, and the graphene nanosheet has a thickness of 5-10 nm.
3. The method of claim 1, further comprising, before the step of vertically growing the copper hydroxide nanorods on the copper substrate by using the chemical oxidation method, washing the copper substrate with hydrochloric acid and water alternately for several times, wherein the copper substrate is a copper sheet, a copper wire mesh or a copper foam.
4. The preparation method of the multilevel-structure graphene according to claim 1, wherein the step of vertically growing the copper hydroxide nanorods on the copper substrate by using a chemical oxidation method to obtain the copper substrate/copper hydroxide nanorod array material specifically comprises the steps of immersing the copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing at room temperature for 1-24 h, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1.
5. the preparation method of the multilevel-structure graphene according to claim 1, wherein the step of calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain the copper substrate/copper oxide nanorod array material specifically comprises calcining the copper substrate/copper hydroxide nanorod array material in an argon atmosphere at 500-600 ℃ for 1-3 h to obtain the copper substrate/copper oxide nanorod array material.
6. The method for preparing graphene with a multilevel structure according to claim 1, wherein the step of reducing the copper substrate/copper oxide nanorod array material by a hydrothermal reduction method to obtain the copper substrate/copper nanorod array material specifically comprises,
preparing a reducing agent solution from sodium hydroxide, a reducing agent and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material.
7. The method according to claim 6, wherein the reducing agent is one of glucose, hydrazine hydrate, sodium borohydride, ascorbic acid and oxalic acid.
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